CN101405308B - Continuous process for the production of vinyl chloride (co)polymers - Google Patents
Continuous process for the production of vinyl chloride (co)polymers Download PDFInfo
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- CN101405308B CN101405308B CN2007800103631A CN200780010363A CN101405308B CN 101405308 B CN101405308 B CN 101405308B CN 2007800103631 A CN2007800103631 A CN 2007800103631A CN 200780010363 A CN200780010363 A CN 200780010363A CN 101405308 B CN101405308 B CN 101405308B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/06—Vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F114/02—Monomers containing chlorine
- C08F114/04—Monomers containing two carbon atoms
- C08F114/06—Vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/001—Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
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Abstract
The present invention relates to polymerization process comprising the steps of: (a) reacting an aqueous suspension comprising initiator, vinyl chloride, and optionally one or more co-monomers in a continuous stirred tank reactor; and (b) further reacting the resulting suspension in at least one second reactor; wherein the conversion level of vinyl chloride in the continuous stirred tank reactor of step (a) is from 10 to 60 wt%.
Description
The present invention relates to a kind of vinylchlorid and method of choosing any one kind of them or multiple comonomer carries out suspension polymerization of making.
Vinylchlorid carries out polymerization through mass polymerization, solution polymerization, letex polymerization or suspension polymerization usually.In bulk polymerization, the liquid portion of reaction mixture mainly contains monomer.The polymkeric substance of gained will be present in the reaction mixture with the solids form that is suspended in the liquid monomer.
In suspension process, the liquid portion of reaction mixture is the suspension-s of monomer in water.Polyreaction is carried out in the monomer droplet that suspends.For this method, be chosen in aqueous phase poorly soluble or at least optimum solvation in monomer those initiators in mutually.
In emulsion polymerisation process, polyreaction is carried out at aqueous phase, forms polymer particle by the monomer that is dissolved in aqueous phase.Also there is monomer droplet, but in these monomer droplets, polymerization can not take place basically.Contrast this method, needs are used water miscible basically and are insoluble to monomeric initiator.
Suspension polymerization usually more preferably than bulk polymerization, this is that and the transformation efficiency that in suspension polymerization, can reach is higher because conduct heat better.The shortcoming of solution polymerization process is need remove from polymkeric substance to desolvate.The shortcoming of emulsion polymerisation process is to need a large amount of tensio-active agents.In addition, the letex polymerization of vinylchlorid generally causes the PVC performance different with other types of polymerization processes.
Compare with the polymerization method of other type, directly do not develop suspension polymerization.If particularly initiator is metered into reactor drum,, then form easily so-called " gel " or " flake " if initiator has low water solubility in temperature of reaction.In this case, initiator is not evenly distributed in the monomer droplet in the time of needs formation significant quantity radical.
US3,004,013 discloses the continuation method that makes vinylchlorid carry out suspension polymerization.This method is used two stirred reactors.Vinyl chloride monomer, lauroyl peroxide, Vilaterm alcohol and water are added first reactor drum, partially polymerized reaction here takes place.In second reactor drum, continue reaction and accomplish reaction.Used polymerization temperature is 50 ℃.The shortcoming of this method is that nearly all superoxide will be retained in the final product; If or be chosen in the system sufficiently long mean residence time to realize low residual peroxide level, then peroxide level with so that the transformation efficiency in second reactor drum will be very low.The latter causes this method infeasible economically.
WO03/054040 discloses a kind of one or more initiators of use makes vinyl chloride monomer and optional other monomer carry out the polymeric method, wherein will be that 0.0001-0.050 hour organic initiators is metered in the polyblend transformation period under polymerization temperature.This document suggestion is carried out polymerization with (partly) continuous mode, wherein uses continuous tubular reactor and adds initiator at the different feed points place of reactor drum, makes that rate of polymerization all is enough up to next decanting point.This method requires a plurality of controls and feed point, so quite complicated.
US4,424,301 have also described this (partly) continuous polymerization method.This document description the multistage polymerization method, wherein use length/diameter than being at least 4 tubular reactor.The polymerization method of this document carries out according to the plug flow pattern, this expression transform level depend on the position in tubular reactor, and along with reaction mixture in tubular reactor process and increase.The shortcoming of tubular reactor is that they are difficult to cleaning, and the stirring operation in tubular reactor is very complicated.But, must between the transition phase of monomeric first 20-50% of add, dynamically mix at least (stirring), thereby obtain to have the for example polymkeric substance of fine granularity distribution of desired properties.During first 20-50% transformation efficiency the coking of reactor wall appears easily, although adopted special processing for example to apply the anti-coking agent.
The purpose of this invention is to provide and a kind ofly make vinylchlorid carry out (being total to) polymeric to improve one's methods.
This purpose realizes through the polymerization method that may further comprise the steps:
(a) make and contain initiator, vinylchlorid and choose any one kind of them or the aq suspension of multiple comonomer reacts in continuous stirred tank reactor; With
(b) gained suspension-s is further reacted at least one second reactor drum;
Wherein the conversion rate of vinyl chloride in the continuous stirred tank reactor of step (a) is 10-60 weight %.
With the polymer phase ratio that obtains through the ordinary method of under identical average polymerization temperature, operating, SE or its multipolymer that method of the present invention and the particularly transform level in continuous stirred tank reactor (CSTR) allow preparation to have higher K value.So the inventive method can be carried out under higher temperature, makes polymerization rate higher, the utilization ratio of production unit increases.Another advantage is to compare with other method of wherein using identical residence time/batch time to reach the same conversion level, and the consumption of initiator reduces.When polyreaction started, promptly during the low-conversion level, the consumption of initiator was significantly higher than the situation when polyreaction is carried out under the given conversion level according to continuous mode.When the inventive method, this startup is only carried out once, and when beginning each new lot, all will pass through this startup according to the method that intermittent mode carries out, so the initiator consumption in continuation method is significantly lower.In addition, compare with the continuation method of under transform level of the present invention, carrying out, the wherein partially polymerized continuation method of carrying out when being lower than 10 weight % transformation efficiencys that is reflected at has consumed more initiator.This for example is at US4, the situation of method described in 424,301.
Another advantage of the inventive method is can have than the charging (for example from CSTR) with the lower temperature of polymerization temperature in the post-reactor through interpolation to obtain extra cooling power.This permission reaches higher rate of polymerization in post-reactor, and overall throughput increases.
In the present invention, the weight ratio between the amount of the amount of " transform level " or " transform level of vinylchlorid " expression polymkeric substance and polymkeric substance and vinyl chloride monomer.If there is comonomer, then transform level is represented the weight ratio between the total amount of amount and vinylchlorid, comonomer and multipolymer of multipolymer.Transform level is represented with weight %.Transform level can use thermal equilibrium in system, to detect, or thermogravimetric analysis is also carried out in the sampling of the aq suspension from reactor drum then.
In the methods of the invention, the transform level in CSTR generally is at least 10 weight %, preferred at least 15 weight %, at least 20 weight % most preferably, and be 60 weight % at the most, preferred 50 weight % at the most, most preferably 40 weight % at the most.Then, the monomer of interpolation is being arranged in the reactor drum polymerization of this first reactor downstream.Transform level in first CSTR is the stable state transform level in the CSTR operate continuously, and selected speed and the selected speed of taking out aqeous suspension from CSTR of adding (copolymerization) monomer, initiator and optional other component to CSTR of this expression has obtained (copolymerization) monomer conversion level required among CSTR.
In one embodiment of the invention; This technology is used at least two the successive stirred-tank reactors (CSTR) that are connected in series; Wherein make and contain initiator, vinylchlorid and choose any one kind of them or the aq suspension of multiple comonomer carries out partial reaction in first CSTR; The suspension-s of gained is added via at least one downstream CSTR, and wherein will be 0.0001-1.0 hour the transformation period under polymerization temperature, preferably 0.0001-0.5 hour at least a initiator is metered into that CSTR that is arranged in first reactor downstream or is arranged at least one CSTR of first reactor downstream.
This embodiment provides a kind of amount of peroxides that is retained in the final product that can make lower and do not have a method of the shortcoming relevant with stirred tube reactor.In addition, most of cooling power of reactor drum can be utilized, and economic feasibility is good.
Second reactor drum can be any reactor drum well known in the art.Generally, second reactor drum is applicable to according to the present invention and prepares polymkeric substance continuously.The example of suitable reactors is continuous stirred tank reactor and tubular reactor.Second continuous stirred tank reactor preferably.
The various reactor drums that in this method, use can have identical size, or they can be of different sizes.The size of reactor drum can confirm that this allows further to optimize the inventive method through required transform level and/or the output in said reactor drum.
If second reactor drum is CSTR, then suspension-s is transported to the inlet of second CSTR from first CSTR, then other reactor drum randomly through being connected in series.This conveying can be used fresh feed pump or through utilizing the pressure gap between each reactor drum to carry out.When upstream reactor during by the liquid completely filled, with the pressure gap on producing from a reactor drum to the transport pipe of next reactor drum automatically, prerequisite is that the fresh feed pump that is positioned at the reactor drum upper reaches surpasses (the highest) vapour pressure.Also can operate one or more not by the reactor drum of completely filled.In this case, can use other source that can between reactor drum, produce pressure gap.If the suspension temperature in a reactor drum is different with the suspension temperature in the next reactor drum, then can produce pressure gap, perhaps, pressure produces pressure gap when reducing at higher transform level.Reactor series preferably comprises 2-5 CSTR.
As selecting or extraly, promoting conveying from a reactor drum to next reactor drum through transferpump.In another embodiment, conveying is to control through the valve that suspension liquid level in the reactor drum is had response, or controls through pressure relief valve.
Also can consider discharging with the discharging of a reactor drum, particularly process step CSTR a) be used to supply two or more can parallel or tactic reactor drum.Can consider that also last reactor drum in reactor sequences is a batch reactor.In this case, one or more reactor drums of front are used to fill batch reactor.In batch reactor, polyreaction is carried out and is accomplished.
In the methods of the invention, water, initiator, vinyl chloride monomer (VCM) and optional comonomers are added among first CSTR continuously.If desired, also can in this CSTR, add the conventional additives that is used for suspension polymerization, for example tensio-active agent, protective colloid, anti-coking agent and pH buffer reagent.The anti-coking agent also can be applied in the reactor drum before technology starts.
These components can add separately among first CSTR.Perhaps, two or more these components can be mixed in pre-reactor, then the gained mixture are added first CSTR.Also can before starting technology, these components be added in one or more reactor drums in advance.
Based on the total monomer weight meter in the suspension-s, VCM concentration is at least 50 weight % preferably, more preferably at least 80 weight %, most preferably from about 100 weight %.
Operable comonomer is those of general type, comprises vinylidene chloride, vinyl-acetic ester, ethene, propylene, vinyl cyanide, vinylbenzene and (methyl) propenoate.As state of the art was known, the polymerization temperature of these technologies had determined the molecular weight (being commonly referred to the K value) of gained (being total to) polymkeric substance to a great extent.
The initiator that adds among first CSTR can be any initiator that is applicable to the chloroethylene polymerization reaction.Preferably, this initiator has 0.0001-1.0 hour transformation period under temperature of reaction, but also can in first CSTR, add one or more initiators the long half-lift of having more.Preferably, initiator has 0.0001-0.5 hour transformation period under temperature of reaction.Also can consider two or more initiators of combination use, wherein at least a initiator has 0.0001-1.0 hour, preferred 0.0001-0.5 hour transformation period under temperature of reaction.The amount that is metered into the initiator among first CSTR is 50-2000ppm preferably, based on the monomeric total mass flow rate meter that gets into this reactor drum.
Continuous stirred tank reactor (or CSTR) is defined as the tank reactor that is equipped with some agitators (for example stirring); To wherein adding reactant and optional other component; And therefrom take out the reaction mixture of gained continuously and/or discontinuously, prerequisite is that CSTR does not operate under plug flow conditions.Plug flow conditions representes that this technology special (Peclet) accurate number in pik is higher than in 50 the reactor drum and operates, this with at US4, the resemble process that carries out in the tubular reactor described in 424,301.Preferably, CSTR is being lower than operation under 20 the Peclet number, and more preferably Peclet number is lower than 15, and more preferably Peclet number is lower than 10 again, and more preferably Peclet number is lower than 5 again, and most preferably Peclet number is lower than 2.Peclet number is that those skilled in the art know and use always, and its implication is for example referring to S.M.Walas, " the 23rd joint: reaction apparatus (ChemicalReactors) "; Perry ' s Chemical Engineers ' Handbook; The 7th edition, McGraw-Hill, 1997.
In one embodiment, each component materials flow can add and/or taking-up with different flow rate.This can cause the different liquid levels of CSTR during technology.Hope is compared with the time average liquid level of CSTR during continuous processing; When (i) continuous processing starts, begin to fill CSTR and between (ii) continuous processing finishes during in the variation of liquid level among the CSTR be not more than the factor 4; More preferably no more than 2, most preferably be not more than 30%.
If necessary, a plurality of CSTR can comprise the geometry of PVC reactor drum at any known intermittence, for example refrigerated baffle.In addition, can use the sectional CSTR that comprises several mixing zones.These mixing zones can through use the multistage radially the pumping impeller produce.
Before introducing CSTR, the one or more chargings (particularly adding the charging among first CSTR) that are metered among the CSTR preferably remain on the temperature lower than suspension temperature among this CSTR.This causes the cooling of this CSTR to improve, thereby permission reaches higher transformation efficiency in the CSTR operation under temperature required.More preferably, said one or more charging remains on the temperature than low at least 10 ℃ of suspension temperature among this CSTR.More preferably, said one or more charging remains on the temperature than low at least 20 ℃ of suspension temperature among this CSTR.Whipping device and/or interchanger can add feeding line and/or add in the metering still, thus optimization efficiency.
Preferably 40-75 ℃ of temperature in first CSTR.
If necessary, can be tubular reactor after a series of CSTR.Preferably, medial temperature in this tubular reactor exceeds at least 1 ℃ than the temperature among the CSTR in downstream, more preferably exceeds at least 2 ℃, more preferably exceeds at least 3 ℃ again.This will have the effect that further is reduced in the residual peroxide level in gained vinylchlorid (being total to) polymkeric substance.
Reaction heat in this tubular reactor itself can (partly) be used for elevated temperature.Elevated temperature also can be used to make the subsequent step of the reacting slurry degassing.
Randomly, can control through the heat transferring medium of the shell circulation process around tubular reactor along the temperature variation of tubular reactor length.Tubular reactor can have the shape of spiral coiled pipe, and the spiral coiled pipe is immersed in (optional stirring) by in the jar of heat transferring medium filling.
Can equal the temperature of first CSTR in the temperature that is arranged in second reactor drum in first CSTR downstream, particularly be arranged in one or more other CSTR reactor drums in first CSTR downstream.Perhaps, the temperature in first CSTR and second reactor drum, particularly one or more other CSTR can be inequality.In one embodiment, the temperature in the CSTR of downstream is lower than the temperature among the previous CSTR, and preferred low at least 2 ℃, more preferably low at least 3 ℃.As stated, this will cause the pressure gap between each reactor drum, thereby promote that suspension-s is transported to next reactor drum from a reactor drum.
In another embodiment, the temperature in the downstream reactor is higher than the temperature in the previous reactor drum, is preferably up to few 3 ℃, is preferably up to few 5 ℃ especially.Because from the cold feed of upstream reactor, this provides the higher cooling power of downstream reactor.This has also reduced the transformation period of the initiator in downstream reactor, thereby reduces residual peroxide level.
Randomly, between two reactor drums, there is interchanger, thereby improves the cooling power of total system.
The initiator that uses in the methods of the invention can be any initiator well known in the art.In one embodiment, it will be that 0.0001-1.0 hour at least a initiator is metered into downstream reactor (in any one) transformation period under polymerization temperature, particularly in second reactor drum.The preferably 0.0001-0.5 hour transformation period of initiator under polymerization temperature, more preferably 0.001-0.4 hour, most preferably 0.01-0.3 hour.In this respect, these initiators are called as " fast initiators ".
Also can consider to be metered into the superoxide activation in the reactor drum in the more downstream that remarkable higher temperature is operated down in the upstream reactor.For this reason, the temperature in downstream reactor exceeds at least 5 ℃ than the temperature of the reactor drum that is metered into initiator, is preferably up to few 8 ℃, is preferably up to few 10 ℃ especially.
Suitable initiator is listed in the following table.Half-lives of initiators under differing temps can confirm through the conventional Study of Thermal Decomposition in monochloro benzene, this be well known to those skilled in the art (referring to for example handbook " initiator that is used for superpolymer ", numbering 10737 is from Akzo Nobel).In the present invention, term " transformation period under polymerization temperature " is illustrated in the transformation period under the top temperature in the suspension temperature in the reactor drum, and prerequisite is that this temperature is no more than 75 ℃.If the temperature of suspension-s surpasses 75 ℃, then the transformation period of term " transformation period under polymerization temperature " when being illustrated in 75 ℃.So if use three reactor drums in the methods of the invention, and the suspension temperature in these reactor drums is respectively 50 ℃, 55 ℃ and 60 ℃, then the transformation period of fast initiators be 60 ℃ preferred 0.0001-1.0 hour down.
Though organo-peroxide is preferred initiator in the methods of the invention, also can use redox initiation system.In this case, reductive agent or oxygenant or the two can be metered into according to the present invention.The speed that is used for redox system formation radical is not to depend on temperature, but depends on the metering rate and the required time of each component mixing of each component usually.So, when confirming the transformation period of redox system under polymerization temperature, must consider the mixing required time of each component.For redox system, the transformation period under polymerization temperature is the transformation period of when having all components of this system and add the conventional mixing time in stirring tank at 0.01 hour, detecting.
But, consider that redox system contains heavy metal and/or unwanted reductive agent usually, initiator of the present invention preferably is not this redox initiation system.
Preferred fast initiators is diisobutyryl peroxide, peroxy neodecanoic acid 1,1-dimethyl--3-hydroxybutyl ester, peroxy NSC 7300 tetramethyl butyl ester, peroxy NSC 7300 tert-pentyl ester and their mixture.Most preferred fast initiators is a diisobutyryl peroxide.
Though be not too preferred, also can except fast initiators, also add one or more transformation period under polymerization temperature and be in the 0.0001-1.0 hour initiator outside the scope.
The total amount that is used for the initiator of the inventive method is in the polymerization method scope commonly used.Generally, use the initiator of 0.01-1 weight %, preferred 0.01-0.5 weight % is based on wanting one or more monomeric weight meters of polymeric.
It should be understood that term " is metered into " is used for being illustrated under the polymerizing condition step that fast initiators is added aq suspension.This metering interpolation can be interrupted or carry out continuously.
If be metered into discontinuously, then with fast initiators according at least 2 parts, preferred at least 10 parts, more preferably at least 30 parts and the reactor drum that most preferably at least 100 parts add CSTR or other type during technology of the present invention.These parts preferably are metered into according to the situation of the interval between each part less than 2 times of mean residence times, are more preferably less than 0.5 times mean residence time, most preferably less than 0.1 times mean residence time.The average content (kg) that mean residence time is defined as in the reactor drum that feeds in raw material adds the overall average flow velocity (kg/hr) of the materials flow in this reactor drum divided by all.
Fast initiators also can be metered into continuously.Perhaps, use the continuous and discontinuous array configuration that is metered into.The example of this combination be the time durations that wherein adds continuously with fast initiators wherein add interrupt during those methods of hocketing.
Preferably, being metered into of fast initiators can be carried out at any suitable reactor inlet place.Can advantageously use the pipeline that is metered into water simultaneously to be metered into fast initiators.Should be noted in the discussion above that if the formation of initiator is enough fast, then can the raw material that be used for said initiator added pipeline or keep container, then from here fast initiators being metered into the reactor drum.Perhaps, still not too preferably, can in aq suspension, add the raw material that is used to prepare fast initiators.
Fast initiators is metered into pure form, or preferred form adding with dilute solution or dispersion liquid.Can use one or more suitable solvents to dilute initiator.Preferably, can easily be removed during the polymkeric substance aftertreatment of these solvents after polymerization technique, or they have the character that can keep as the resistates in the final polymkeric substance.In addition, these solvents preferably do not have disadvantageous effect to the thermostability of institute's dissolved fast initiators, and this can confirm through analyzing the half life temperature of initiator in said solvent.The example of suitable solvent is a Permethyl 99A..If be metered into initiator dispersion, then dispersion liquid can be a fast initiators itself, or the solution of fast initiators, preferably the solution in said suitable solvent.Preferably, dispersion liquid is an aqueous dispersion.More preferably, dispersion liquid is that medium droplet size is lower than 10 microns aqueous dispersions.This allows initiator to be dispersed in better in the VCM drop.
Preferably, fast initiators is with 1-70 weight %, the more preferably concentration measurement adding of 20-65 weight %.
Preferably at least a, more preferably the whole initiator that is metered into has in water the solubleness of 5ppm at least, more preferably 50ppm at least, most preferably 200ppm at least.This will improve the mass transfer of initiator to the VCM drop, thereby reduce the formation of flake.
Except initiator; Can to second with other reactor drum in add other component; For example VCM, comonomer, water, tensio-active agent, protective colloid (for example Z 150PH), anti-coking agent, pH buffer reagent, dispersion agent and other add the additive among the PVC preparation technology usually; Thereby obtain known effect in conventional PVC suspension polymerization, for example influence porosity, tap density, granularity etc.
Preferably 1-10 hour the suspension-s residence time in the series reaction device.
After leaving last reactor drum, (being total to) polymer slurry of gained is collected in the blow-down vessel, be transported to (continuously) degassing and/or drying stage then.One of advantage of the inventive method is: combine the processing of successive downstream, no longer need in blow-down vessel, collect (being total to) polymer slurry.But, randomly, can use blow-down vessel.In this case, can in blow-down vessel, carry out the part degassing.
In one embodiment of the invention, monomer conversion level (that is, the transform level in downstream reactor) is lower than the final transform level in conventional PVC suspension polymerization process, and this is attractive economically.Generally, the total conversion rate level is lower than 80 weight %, preferably is lower than 75 weight %, most preferably is lower than 70 weight %.The advantage of lower final transform level is that thermostability and the colour stability of gained PVC is improved.In addition, reactor capacity is improved, and this is because the reactive component latent heat of the monomer (kg) that has transformed by unit weight is improved.
Also consider extra water is added in one or more said reactor drums, thereby improve cooling power (directly cooling) and improve rate of polymerization and throughput.
In specific embodiments; At least one reactor drum that uses in the methods of the invention, preferred total reactor are (promptly; First CSTR and one or more second reactor drum, particularly other CSTR or batch reactor) be equipped with (backflow) condensing surface so that extra cooling to be provided.
In the embodiment that comprises more than a CSTR, the backflow of any of these condensing surface is returned another reactor drum.Preferably, can turn back to the more reactor drum at the upper reaches, most preferably turn back to first CSTR from the backflow of the condensing surface of the one or more reactor drums that are positioned at first CSTR downstream.
In another embodiment of the invention, the reactor drum at least downstream is equipped with such condensing surface, and wherein refluxing turns back to any one more reactor drum at the upper reaches.This will help under so-called pressure reduction condition, to operate the reactor drum in downstream, and promptly the pressure in this reactor drum is lower than the condition of vinyl chloride monomer vapour pressure.This will compensate the influence that the residence time distributes, because this permission is dissolved in aqueous phase from the monomer that is rich in the monomeric drop.Make backflow turn back to any performance that another reactor drum also can influence gained (being total to) polymkeric substance, for example porosity and tap density from condensing surface.
The various startups and the parking procedure of continuous processing be can limit, thereby the economy and the quality product of technology optimized.In one embodiment, for example, be positioned at the reactor drum at the CSTR upper reaches of step a), preferred CSTR operates under the transformation efficiency that is lower than 10 weight %.
After polymerization, (being total to) polymkeric substance of gained will carry out aftertreatment according to the prior art ordinary method.(being total to) polymkeric substance that obtains through the inventive method can for example carry out conventional drying and screening step.
In the methods of the invention, can prepare (being total to) polymkeric substance with superior heat-stability.This thermostability can use the experiment baking oven to detect according to method ASTM1925.(being total to) polymkeric substance does not almost have variable color when carrying out melt-processed step (for example forming moulded products).
Through embodiment the present invention is described below.
Embodiment
Embodiment 1
Suspension PVC polymerization technique uses two internal diameters to carry out as the stainless steel 10L B ü chi autoclave of 18cm continuously.Each autoclave has: a baffle plate; TP; Account for the whisking appliance of two flat lodicules of container diameter 1/3, their about stirrer diameter of being separated by; X-former, level sensor, vinyl chloride monomer (VCM) feeding line, nitrogen purge line, water feeding line and water/PVA feeding line, and peroxide feed line.
The volume pump that is used for VCM, water, PVA solution and initiator is connected with first reactor drum.Second initiator volume pump is connected with second reactor drum.
Two reactor drums connect via 10mm stainless steel pipeline, from the top of the dipping tube first reactor drum via second reactor drum of automatic ball valve arrival.Second reactor drum also comprises dipping tube, is connected with 300ml measuring container between two automatic ball valves via the 10mm steel pipe.Measuring container is used for polymer slurry partly is discharged to stripping stage.
First reactor drum is equipped with the 2L water that contains about 0.47g Alcotex B72 (PVA is from Harco) and 0.8gGohsenol GH23 (PVA is from Nippon Gohsei).Reactor drum clings to about 15 with nitrogen pressure subsequently.Then, reactor drum was vacuumized 3 minutes, and add the VCM of 700g at 75mmHg.
Second reactor drum be according to identical procedure operation, but different be that the 2L water that contains half half amount VCM (300-350g) of amount PVA peace treaty is housed.
Stirring velocity in two reactor drums all is 800rpm.
When reactor drum has been heated to required temperature of reaction; The metering that starts VCM, water, PVA and superoxide is added; In this case, use together the VCM flow velocity of 1.35kg/h and altogether 3L water/h and PVA according to ratio based on the 700ppm Alcotex:115ppmGohsenol of VCM/h meter.
Used initiator is Tx187-W26 (26% emulsion of diisobutyryl peroxide in water is from Akzo Nobel Polymer Chemicals) in this method.Initiator adds 45 minutes (being emulsified in the pure diisobutyryl peroxide in the water) with the 1.56g/h metering.Then, metering rate is set at 0.31g/h.During the fs, first reactor drum reaches pressure drop in comparatively high temps (promptly 59 ℃ replace 57 ℃) operation down up to second reactor drum.Then, these two reactor drums are all remained on 57 ℃.When reaching predeterminated level (65%), open self-acting valve, and the slurries of first consumption are transported to second reactor drum.From begin metering interpolation this moment to second reactor drum.Reduce up to pressure, be metered into 1.56g/h (pure diisobutyryl peroxide), metering rate is reduced to 0.6g/h then, is the 0.5-1 crust thereby in second reactor drum, keep average pressure drop.Therefore, in steady state process, for the VCM of 1.35kg/h, total initiator metering rate is 0.39/h (a pure diisobutyryl peroxide).
When reaching second predeterminated level (65%) in the reactor drum at every turn, open the self-acting valve that leads to measuring container, and fixed amount is transported to collection container, here with the slurries degassing and find time.In this way, in two reactor drums, all kept more or less constant level (± 5%).The overall average residence time in two reactor drums (between two reactor drums, dividing equally) is 2.4 hours.
After reaching stable state, the size-grade distribution of prepared PVC is held constant at D
50=150 microns (volume mean diameter detects with the Coulter telltale).The DOP porosity is 23%.The K value of gained PVC is 69, and when using conventional batch technology, generally is about 67 in the K of 57 ℃ of PVC value.
Embodiment 2
In embodiment 2, packing at first reactor drum contains the 3L water of 0.95g Alcotex B72,0.16gGohsenol GH23 and 1350g VCM.Pack at second reactor drum and to contain the 3L water of 0.48gAlcotex B72,0.08g Gohsenol GH23 and 300g VCM.The operation of this embodiment is identical with the operation of embodiment 1.
Embodiment 3
According to operating with embodiment 2 identical modes, different is in second reactor drum also based on the VCM meter that per hour is metered into, and is metered into PVA with the speed of 350ppm Alcotex B72 and 60ppm GohsenolGH23.
Transform level among the embodiment 1-3 in first reactor drum and superoxide total flow are listed in the table 1.
Table 1
| Embodiment | Transformation efficiency in first reactor drum (weight %) | Superoxide total flow (ppm is based on VCM) | Productive rate (%) |
| 1 | 28 | 780 | 67 |
| 2 | 26 | 810 | 64 |
| 3 | 21 | 780 | 64 |
The various performances of PVC product in table 2, have been listed.
Table 2
| Embodiment | The K value | D 50 (μm) | Tap density (g/l) | Porosity (%) |
| 1 | 69 | 151 | 430 | 23 |
| 2 | 71 | 150 | 457 | 22 |
| 3 | 70 | 150 | 510 | 19 |
Claims (11)
1. polymerization method, this method may further comprise the steps:
(a) make and contain initiator, vinylchlorid and choose any one kind of them or the aq suspension of multiple comonomer reacts in continuous stirred tank reactor; With
(b) gained suspension-s is further reacted at least one second reactor drum;
Wherein the conversion rate of vinyl chloride level in the continuous stirred tank reactor of step (a) is 10-40 weight %.
2. according to the polymerization method of claim 1, wherein said transform level is 20-40 weight %.
3. according to the polymerization method of claim 1 or 2, wherein second reactor drum is selected from continuous stirred tank reactor, tubular reactor or batch reactor.
4. according to the polymerization method of claim 1 or 2, wherein polymerization method carries out continuously.
5. according to the polymerization method of claim 1 or 2; Wherein use at least two continuous stirred tank reactors that are connected in series; Wherein this method is carried out continuously; And the aq suspension that will obtain from step a) adds via at least one downstream continuous stirred tank reactor, and wherein will be that 0.0001-0.5 hour at least a initiator is metered into that continuous stirred tank reactor that is arranged in first reactor downstream or is arranged at least one continuous stirred tank reactor of first reactor downstream the transformation period under polymerization temperature.
6. according to the polymerization method of claim 1 or 2, wherein said at least one continuous stirred tank reactor is equipped with condensing surface.
7. according to the polymerization method of claim 1 or 2, the one or more continuous stirred tank reactors that wherein are positioned at first continuous stirred tank reactor downstream are equipped with reflux exchanger, and the backflow of wherein said condensing surface flows to the more reactor drum at the upper reaches.
8. according to the polymerization method of claim 7, the backflow of wherein said condensing surface flows to first continuous stirred tank reactor.
9. according to the polymerization method of claim 1 or 2, the transformation period of initiator under polymerization temperature that wherein is metered into that continuous stirred tank reactor that is arranged in first reactor downstream or is arranged at least one second reactor drum of first reactor downstream is 0.001-0.4 hour.
10. according to the polymerization method of claim 9, wherein said second reactor drum is a continuous stirred tank reactor.
11. according to the polymerization method of claim 10, the transformation period of initiator under polymerization temperature that wherein is metered into that continuous stirred tank reactor that is arranged in first reactor downstream or at least one continuous stirred tank reactor that is arranged in first reactor downstream is 0.01-0.3 hour.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
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| EP06111682 | 2006-03-24 | ||
| EP06111682.8 | 2006-03-24 | ||
| US78752806P | 2006-03-31 | 2006-03-31 | |
| US60/787,528 | 2006-03-31 | ||
| PCT/EP2007/052612 WO2007110350A1 (en) | 2006-03-24 | 2007-03-20 | Continuous process for the production of vinyl chloride (co)polymers |
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| CN101405308B true CN101405308B (en) | 2012-02-15 |
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| US (1) | USRE45940E1 (en) |
| CN (1) | CN101405308B (en) |
| BR (1) | BRPI0709144B1 (en) |
| ES (1) | ES2599581T3 (en) |
| HU (1) | HUE030197T2 (en) |
| MY (1) | MY148304A (en) |
| PL (1) | PL1999169T3 (en) |
| RU (1) | RU2434885C2 (en) |
| SA (1) | SA07280130B1 (en) |
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| KR101941098B1 (en) * | 2016-04-25 | 2019-01-22 | 주식회사 엘지화학 | Method for preparing vinyl chloride polymer and vinyl chloride polymer prepared therefrom |
| CN114181336A (en) * | 2021-12-16 | 2022-03-15 | 安徽天辰化工股份有限公司 | Ultra-small particle size PVC seed and preparation method thereof |
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| US3004013A (en) * | 1954-04-28 | 1961-10-10 | Detrex Corp | Method for producing finely divided polyvinyl chloride |
| CN1031089A (en) * | 1987-03-17 | 1989-02-15 | 阿托化学公司 | Suspension emulsion polymerization preparation is insoluble to the method for the polymkeric substance and the multipolymer of monomer whose or comonomer composite |
| CN1514847A (en) * | 2001-06-15 | 2004-07-21 | ɳ�ػ�����ҵ��˾ | Process for polymerization of polyvinylchloride |
| WO2004096871A1 (en) * | 2003-05-01 | 2004-11-11 | Akzo Nobel N.V. | Increased polymerization reactor output by using a specific initiator system |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5693710A (en) | 1979-12-28 | 1981-07-29 | Toagosei Chem Ind Co Ltd | Continuous suspension polymerization of vinyl chloride |
| JPS56118407A (en) | 1980-02-26 | 1981-09-17 | Toagosei Chem Ind Co Ltd | Suspension polymerization method of vinyl chloride |
| DE3018643C2 (en) | 1980-05-16 | 1982-07-08 | Chemische Werke Hüls AG, 4370 Marl | Process for the production of impact-resistant modified styrene polymers |
| DE3029907A1 (en) | 1980-08-07 | 1982-03-18 | Hoechst Ag, 6000 Frankfurt | CONTINUOUS METHOD AND DEVICE FOR PRODUCING A VINYL CHLORIDE POLYMERISATE IN AQUEOUS SUSPENSION |
| GB8300889D0 (en) * | 1983-01-13 | 1983-02-16 | Bp Chem Int Ltd | Steric stabilisation of pvc particles against agglomeration |
| JPH0710892B2 (en) * | 1985-03-08 | 1995-02-08 | 鐘淵化学工業株式会社 | Manufacturing method of vinyl chloride resin |
| KR100417066B1 (en) | 2001-01-08 | 2004-02-05 | 주식회사 엘지화학 | Method for preparing thermoplastic resin having superior heat resistance |
| UA77245C2 (en) | 2001-12-21 | 2006-11-15 | Акцо Нобель Н.В. | Process for polymerization of mixture containing vinylchloride monomer |
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2007
- 2007-03-20 RU RU2008142137/04A patent/RU2434885C2/en not_active IP Right Cessation
- 2007-03-20 PL PL07727089T patent/PL1999169T3/en unknown
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3004013A (en) * | 1954-04-28 | 1961-10-10 | Detrex Corp | Method for producing finely divided polyvinyl chloride |
| CN1031089A (en) * | 1987-03-17 | 1989-02-15 | 阿托化学公司 | Suspension emulsion polymerization preparation is insoluble to the method for the polymkeric substance and the multipolymer of monomer whose or comonomer composite |
| CN1514847A (en) * | 2001-06-15 | 2004-07-21 | ɳ�ػ�����ҵ��˾ | Process for polymerization of polyvinylchloride |
| WO2004096871A1 (en) * | 2003-05-01 | 2004-11-11 | Akzo Nobel N.V. | Increased polymerization reactor output by using a specific initiator system |
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| BRPI0709144B1 (en) | 2018-03-13 |
| BRPI0709144A2 (en) | 2011-06-28 |
| ES2599581T3 (en) | 2017-02-02 |
| SA07280130B1 (en) | 2010-11-02 |
| RU2434885C2 (en) | 2011-11-27 |
| MY148304A (en) | 2013-03-29 |
| PL1999169T3 (en) | 2017-02-28 |
| ZA200809109B (en) | 2009-07-29 |
| RU2008142137A (en) | 2010-04-27 |
| TW200745172A (en) | 2007-12-16 |
| CN101405308A (en) | 2009-04-08 |
| HUE030197T2 (en) | 2017-04-28 |
| USRE45940E1 (en) | 2016-03-22 |
| TWI439471B (en) | 2014-06-01 |
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